CN115283881A - Soldering flux, high-viscosity paste thereof, preparation method of high-viscosity paste, solder paste and application of solder paste - Google Patents
Soldering flux, high-viscosity paste thereof, preparation method of high-viscosity paste, solder paste and application of solder paste Download PDFInfo
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- CN115283881A CN115283881A CN202211039608.6A CN202211039608A CN115283881A CN 115283881 A CN115283881 A CN 115283881A CN 202211039608 A CN202211039608 A CN 202211039608A CN 115283881 A CN115283881 A CN 115283881A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3613—Polymers, e.g. resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
Abstract
The invention discloses a soldering flux, a high-viscosity paste body of the soldering flux, a preparation method of the high-viscosity paste body, a solder paste and application of the solder paste. The preparation method of the high-viscosity paste comprises the following steps: mixing 120-160 parts of resin acid monomer and 40-80 parts of cross-linking agent according to parts by weight to perform esterification cross-linking reaction to generate an esterification cross-linking product, wherein the resin acid monomer has at least two carboxyl groups; the cross-linking agent is an alcohol having at least two hydroxyl groups; and mixing the esterified crosslinking product with a paste forming solvent according to the mass ratio of 150. The high-viscosity paste is prepared by the preparation method. The high-viscosity low-residue soldering flux comprises the high-viscosity paste. The preparation method of the soldering flux is used for preparing the soldering flux. The solder paste comprises the soldering flux. The soldering flux and the solder paste provided by the application have the advantages that the soldering flux and the solder paste comprise the high-viscosity paste provided by the application, are high in viscosity, are not prone to collapse, and do not have the phenomenon of residual or carbon deposition after soldering.
Description
Technical Field
The invention relates to the technical field of welding materials, in particular to a soldering flux, a high-viscosity paste body of the soldering flux, a preparation method of the high-viscosity paste body, a solder paste and application of the solder paste.
Background
The traditional electronic component welding method is usually adopted for welding, and soldering flux is generally required to be used in the soldering process to improve the welding quality. Common soldering flux is generally solid or liquid, wherein the solid soldering flux is generally compounded by rosin and an active agent, and the liquid soldering flux takes an organic solvent as a carrier and a certain amount of active components are added. The solid soldering flux is generally filled into a hollow tin wire as a flux core, the content is fixed, and the dosage can not be adjusted at will. The liquid soldering flux is generally matched with a tin wire for use, but the liquid soldering flux has the defects of easy volatilization, dripping of the soldering flux due to insufficient viscosity in the using process and the like. Therefore, researchers develop the paste soldering flux, and the problems that the using amount of the soldering flux cannot be adjusted at will, and the soldering flux is easy to volatilize and sticky are solved primarily. Meanwhile, the paste soldering flux and the powder tin solder are mixed to prepare the tin paste, so that the welding process is greatly simplified. Under the trend of labor shortage and rising expenditure of manpower cost, a lot of enterprise users try to introduce point-coating solder paste in hot-air welding to realize automation of spot welding. However, under the hot air welding, the solder paste is easy to have serious thermal collapse and is easy to be blown away by hot air due to insufficient viscosity.
Thixotropic or coupling agents are often added by many researchers to improve the storage and slump resistance during use of paste fluxes and solder pastes. The patent application No. 201610503112.8 entitled "a high stability flux paste" and the patent application No. 201110443581.2 entitled "a paste flux preparation method" all use thixotropic agents to alleviate the delamination or collapse of the paste or solder paste, as is the case with most other patents. The thixotropic agent or the coupling agent is generally composed of a high molecular organic substance or an inorganic salt, has no effect on improving the welding performance, but can cause serious postweld residue due to high boiling point. Thixotropic or coupling agents are more likely to slow the demixing or collapse of a paste or solder paste by physical thickening, which tends to require more severe storage conditions (e.g., low temperature, drying) and even performance failures due to environmental changes (e.g., temperature, air humidity).
In view of this, the present application is specifically proposed.
Disclosure of Invention
The invention aims to provide a soldering flux, a high-viscosity paste body of the soldering flux, a preparation method of the high-viscosity paste body, a solder paste and application of the solder paste.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing a high viscosity paste for a flux, comprising:
mixing 120-160 parts of resin acid monomer and 40-80 parts of cross-linking agent according to parts by weight for esterification and cross-linking reaction to generate an esterification and cross-linking product, wherein the resin acid monomer is selected from at least one of KR610 rosin, dimerized rosin 95, dodecanedioic acid, sebacic acid and tridecanedioic acid; the cross-linking agent comprises at least one of propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol;
and mixing the esterified crosslinking product with a paste forming solvent according to the mass ratio of 150.
In an alternative embodiment, the esterified cross-linked product is mixed with the paste-forming solvent in the following manner:
heating the esterified cross-linked product to 70-160 ℃, and then dropwise adding the esterified cross-linked product into a paste solvent while stirring;
preferably, the paste forming solvent is selected from at least two of 2-ethyl-1,3-hexanediol, tetraethylene glycol dimethyl ether, diethylene glycol, 2-methyl-2,4-pentanediol, and triethylene glycol dimethyl ether.
In an alternative embodiment, before the esterification crosslinking reaction, the method further comprises: recrystallizing the resin acid monomer;
the recrystallization mode is as follows: the resin acid monomer and the recrystallization solvent are mixed and heated to 50-120 ℃ according to the mass ratio of 80-160, are uniformly stirred and mixed, and are subjected to a recrystallization step to obtain a composite paste containing the resin acid monomer;
mixing the resin acid monomer and the cross-linking agent is to mix the compound paste and the cross-linking agent;
preferably, the resin acid monomer is heated to 100-180 ℃ for melting before being mixed with the recrystallization solvent, and is cooled after being stirred for 0.5-1 h; the resin acid monomer mixed with the recrystallization solvent is a resin acid monomer which is heated, melted and cooled;
preferably, the heating mode is heating by a silicone oil bath;
preferably, the recrystallization solvent is selected from at least one of dioxane, carbon tetrachloride and petroleum ether.
In an alternative embodiment, the esterification crosslinking reaction by mixing the resin acid monomer with the crosslinking agent is:
heating the resin monomer to 120-150 ℃, continuously dispersing, stirring and dripping the cross-linking agent at the temperature, adding 0.01-0.03 part of catalyst after the dripping of the cross-linking agent is finished for 20-40 min, and continuously stirring for 3-6 h;
preferably, the catalyst is concentrated sulfuric acid;
preferably, the stirring rate is 1000 to 1500r/min.
In an optional embodiment, the esterification crosslinking reaction is performed to obtain a light yellow reaction solution, the esterification crosslinking reaction further includes extracting an esterification crosslinking product from the light yellow reaction solution, and the method for extracting the esterification crosslinking product includes:
distilling the light yellow reaction liquid under reduced pressure, and cooling to obtain a yellowish white solid primary esterification crosslinking product;
washing the primary esterification crosslinking product by using deionized water, and then drying under reduced pressure to obtain an esterification crosslinking product;
preferably, the drying temperature is 45 to 65 ℃.
In a second aspect, the present invention provides a highly viscous paste for a soldering flux, which is prepared by the preparation method according to any one of the above embodiments.
In a third aspect, the invention provides a high-viscosity low-residue soldering flux, which comprises the following components in parts by weight: 100 parts of the high-viscosity paste according to the previous embodiment, 10-20 parts of organic acid activator, 5-10 parts of surfactant and 2-15 parts of corrosion inhibitor; the organic acid active agent is selected from at least one of 2,2-dimethylolpropionic acid, succinic acid, dimethylolpropionic acid, ricinoleic acid and 2-picolinic acid, the surfactant is selected from at least one of ST-400, polyethylene glycol octyl phenyl ether, dibromobutylene glycol and 2-ethylhexyl phosphate, and the corrosion inhibitor is selected from at least one of 1,2,3-benzotriazole, 2-methyl benzimidazole and benzimidazole;
preferably, the organic acid active agent is selected from at least two of 2,2-dimethylolpropionic acid, succinic acid, dimethylolpropionic acid, ricinoleic acid and 2-picolinic acid.
In a fourth aspect, the present invention provides a method for preparing a high viscosity and low residue flux according to the foregoing embodiment, including:
heating the high-viscosity paste to 70-100 ℃, and adding the organic acid activator, the surfactant and the corrosion inhibitor while stirring; stirring and mixing for 1.5-2.5 h, cooling, and aging in a low-temperature drying environment at 2-5 ℃ for 20-30 h to obtain the high-viscosity low-residue soldering flux.
In a fifth aspect, the present invention provides a solder paste including the high viscosity and low residue soldering flux of the foregoing embodiment or the high viscosity and low residue soldering flux prepared by the preparation method of the foregoing embodiment.
In a sixth aspect, the present invention provides a high viscosity and low residue flux according to the foregoing embodiment, a high viscosity and low residue flux prepared by the preparation method according to the foregoing embodiment, or a solder paste according to the foregoing embodiment for use in soldering.
The invention has the following beneficial effects:
the preparation method of the high-viscosity paste body provided by the invention adopts the resin acid monomer containing at least two carboxyl groups and the cross-linking agent containing two hydroxyl groups to carry out esterification cross-linking reaction, and the cross-linking agent links the molecules of the resin acid monomer into a net shape or even a three-dimensional net shape; the paste body has a net-shaped and three-dimensional net-shaped structure, when the paste body is used as a soldering flux or a solder paste, the paste body can keep the uniform distribution of an active agent, can effectively prevent the settlement and agglomeration of metal powder, improves the viscosity of the solder paste, has good collapse resistance, does not have obvious fluidity under the action of hot wind, and is particularly suitable for hot wind spot coating welding. The main body of the paste is obtained by reacting a resin monomer containing a carboxyl functional group with a dihydric alcohol, a coupling agent or a thixotropic agent used in the common paste is not required to be added, and the phenomena of post-welding residue and post-welding carbon deposition are greatly reduced. Under the high temperature environment of welding, the paste decomposes the high molecular polymer containing carboxyl again, and the carboxyl can effectively remove the metal oxide film and improve the welding performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a cross-sectional metallographic view of a solder joint of solder paste prepared by the paste flux of the present invention;
FIG. 2 is a vertical cross-sectional metallographic view of a solder joint of solder paste prepared by the paste flux of the present invention;
FIG. 3 is a picture of a solder joint of solder paste prepared by the paste flux of the present invention;
fig. 4 is a picture of a welding spot after welding of a commercial common solder paste.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following describes the soldering flux and the high-viscosity paste thereof provided by the embodiments of the present application, and the preparation method, the solder paste and the application thereof in detail.
The embodiment of the application provides a preparation method of a high-viscosity paste for soldering flux, which comprises the following steps:
mixing 120-160 parts of resin acid monomer and 40-80 parts of cross-linking agent according to parts by weight for esterification and cross-linking reaction to generate an esterification and cross-linking product, wherein the resin acid monomer is selected from at least one of KR610 rosin, dimerized rosin 95, dodecanedioic acid, sebacic acid and tridecanedioic acid; the cross-linking agent comprises at least one of propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol;
the esterification crosslinking product and a recrystallization solvent are mixed according to the mass ratio of 150 to 30 ℃ to 160 ℃, stirred for 1 to 3 hours and cooled to obtain high-viscosity paste, and the paste forming solvent is at least one selected from 2-ethyl-1,3-hexanediol, tetraethylene glycol dimethyl ether, diethylene glycol, 2-methyl-2,4-pentanediol and triethylene glycol dimethyl ether.
In the preparation method provided by the embodiment of the application, the resin acid monomer at least containing two carboxyl groups and the cross-linking agent containing two hydroxyl groups are subjected to esterification cross-linking reaction, and the cross-linking agent links the molecules of the resin acid monomer into a net shape or even a three-dimensional net shape; the paste body has a net-shaped and three-dimensional net-shaped structure, when the paste body is used as the soldering flux or the solder paste, the uniform distribution of the active agent can be kept, the settlement and the agglomeration of metal powder can be effectively prevented, the viscosity of the solder paste is also improved, the paste body has good collapse resistance, and the obvious fluidity can not appear under the action of hot wind. The main body of the paste is obtained by reacting a resin monomer containing a carboxyl functional group with a dihydric alcohol, so that a coupling agent or a thixotropic agent used in the common paste is not required to be added, and the phenomena of post-welding residue and post-welding carbon deposition are greatly reduced. Under the high temperature environment of welding, the paste decomposes the high molecular polymer containing carboxyl again, and the carboxyl can effectively remove the metal oxide film and improve the welding performance.
Further, the preparation method of the high-viscosity paste body comprises the following steps:
s1, recrystallizing resin acid monomer
Heating the resin acid monomer to 100-180 ℃ for melting, stirring for 0.5-1 h, and cooling;
mixing and heating the heated and cooled resin acid monomer and a recrystallization solvent to 50-120 ℃ according to the mass ratio of 80-160, uniformly stirring and mixing, and performing recrystallization to obtain a composite paste containing the resin acid monomer;
preferably, in order to achieve a more stable heating effect, the heating manner is heating by a silicone oil bath.
Preferably, in order to ensure that the prepared high-viscosity paste can better realize low residue when applied to the soldering flux, and can realize the dissolution of resin acid monomers, a better recrystallization temperature gradient is selected, and the recrystallization solvent is selected from at least one of dioxane, carbon tetrachloride and petroleum ether.
The resin acid monomer is recrystallized, which is equivalent to the purification of the resin acid monomer, and the high-viscosity paste obtained by the crosslinking reaction of the recrystallized resin acid monomer is applied to the soldering flux, so that the soldering effect is better.
S2, esterification and crosslinking
According to the weight portion, 120-160 portions of resin acid monomer and 40-80 portions of cross-linking agent are mixed, and the mixture is mixed for esterification and cross-linking reaction to generate an esterification cross-linking product.
The resin acid monomer is selected from at least one of KR610 rosin, dimerized rosin 95, dodecanedioic acid, sebacic acid and tridecanedioic acid; the cross-linking agent comprises at least one of propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol.
Preferably, the reaction of the resin acid monomer with the crosslinking agent is effected in a manner that:
heating 120-160 parts of composite paste to 120-150 ℃, stirring at high speed for dispersion at the temperature, dripping 40-80 parts of cross-linking agent while stirring, adding 0.01-0.03 part of catalyst after dripping the cross-linking agent for 20-40 min, and continuously stirring for 3-6 h;
preferably, the catalyst is concentrated sulfuric acid; the concentrated sulfuric acid is preferably analytical grade concentrated sulfuric acid.
Preferably, the stirring speed is 1000-1500 r/min to ensure efficient and sufficient reaction.
S3, extraction of esterified and crosslinked products
Obtaining a light yellow reaction liquid after esterification crosslinking reaction, and distilling and cooling the light yellow reaction liquid under reduced pressure to obtain a yellowish-white solid primary esterification crosslinking product;
the primary esterified crosslinked product was washed with deionized water and then dried under reduced pressure to give an esterified crosslinked product as a white solid.
Preferably, the drying temperature is 45-65 ℃ to ensure sufficient drying without affecting the structure and performance of the esterified crosslinking product.
S4, preparing paste
And mixing the esterified crosslinking product with a paste forming solvent according to the mass ratio of 150.
Preferably, in order to ensure that the prepared high-viscosity paste with good dispersion uniformity and stable performance of the esterified cross-linked product is prepared, the mode of mixing the esterified cross-linked product with the recrystallization solvent is as follows: heating the esterified cross-linked product to 70-160 ℃, and then dropwise adding a recrystallization solvent into the esterified cross-linked product while stirring.
Because the paste forming solvents have different volatilization temperatures, and the welding process is a temperature rise process, in order to ensure that the soldering flux or the solder paste applied to the high-viscosity paste during welding has a wider range of temperatures for releasing active substances and corrosion inhibitors and a wider range of storage temperatures, the paste forming solvents are preferably selected from at least two of 2-ethyl-1,3-hexanediol, tetraethylene glycol dimethyl ether, diethylene glycol, 2-methyl-2,4-pentanediol and triethylene glycol dimethyl ether.
The embodiment of the application also provides a high-viscosity paste for the soldering flux, which is prepared by adopting the preparation method provided by the embodiment of the application.
The embodiment of the application also provides a high-viscosity low-residue soldering flux, which comprises the following components in parts by weight: 100 parts of the high-viscosity paste, 10-20 parts of organic acid activator, 5-10 parts of surfactant and 2-15 parts of corrosion inhibitor.
The organic acid activator is at least one of 2,2-dimethylolpropionic acid, succinic acid, dimethylolpropionic acid, ricinoleic acid and 2-picolinic acid.
Since the organic acid active agents have different volatilization temperatures and the soldering process is a temperature rise process, in order to enable the soldering flux to have a wider range of temperature for releasing the organic acid active agents and a wider range of storage temperature during soldering, preferably, the organic acid active agents are selected from at least two of 2,2-dimethylolpropionic acid, succinic acid, dimethylolpropionic acid, ricinoleic acid and 2-picolinic acid.
The surfactant is selected from at least one of ST-400, polyethylene glycol octyl phenyl ether, dibromobutylene glycol and 2-ethylhexyl phosphate.
The corrosion inhibitor is at least one of 1,2,3 benzotriazole, 2-methyl benzimidazole and benzimidazole.
The flux provided by the embodiment is prepared from the appropriate amount of the high-viscosity paste provided by the embodiment, so that the active agent in the flux is uniformly distributed, the sedimentation and agglomeration of metal powder do not exist, the viscosity of the flux is higher, the flux has good collapse resistance, no obvious fluidity appears under the action of hot air, and the flux is particularly suitable for hot air spot welding. The main body of the high-viscosity paste is obtained by reacting a monomer containing a carboxyl functional group with a dihydric alcohol, so that a coupling agent or a thixotropic agent used in common paste is not required to be added, and the soldering flux has no or less residue and carbon deposition after soldering; under the high temperature environment of welding, the paste decomposes the high molecular polymer containing carboxyl again, and the carboxyl can effectively remove the metal oxide film and improve the welding performance. Therefore, the soldering flux provided by the embodiment of the application has a good soldering effect.
The embodiment of the application also provides a preparation method of the high-viscosity low-residue soldering flux, which comprises the following steps:
heating the high-viscosity paste to 70-100 ℃, and adding the organic acid activator, the surfactant and the corrosion inhibitor while stirring; stirring and mixing for 1.5-2.5 h, cooling, and placing in a low-temperature drying environment at 2-5 ℃ for 20-30 h to obtain the high-viscosity low-residue soldering flux.
The preparation method can prepare the high-viscosity low-residue soldering flux provided by the embodiment of the application.
The embodiment of the application also provides a solder paste which comprises the high-viscosity low-residue soldering flux or the high-viscosity low-residue soldering flux prepared by the preparation method.
The solder paste provided by the embodiment of the application has the same advantages as the high-viscosity low-residue soldering flux provided by the embodiment of the application.
The embodiment of the application also provides the high-viscosity low-residue soldering flux, the high-viscosity low-residue soldering flux prepared by the preparation method or the application of the solder paste in soldering.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a high-viscosity low-residue soldering flux, which comprises the following steps:
(1) Heating 60g of dimerized rosin 95 and 70g of tridecanedioic acid to 150 ℃, keeping the temperature, fully stirring for 1 hour to obtain a light yellow liquid, and cooling; adding 100g of petroleum ether into the light yellow liquid, heating to 70 ℃, uniformly stirring, and cooling to obtain a recrystallized crystal which is a composite paste.
(2) The prepared composite paste was taken out and heated to 130 ℃, stirred using a stirrer with dispersion, and 25g of propylene glycol and 28g of 1,3-butanediol were slowly added dropwise. The stirring speed is adjusted to 1200r/min, after stirring dispersion for 0.5h, 0.2g of concentrated sulfuric acid is added dropwise by a test tube and stirring is continued. After 5h, the stirring is stopped, a yellow reaction solution is obtained after cooling, and the yellow reaction solution is distilled under reduced pressure and cooled to obtain a light yellow solid. The light yellow solid is powdered and washed by deionized water, and then dried under reduced pressure at the drying temperature of 50 ℃ to obtain yellow white solid powder.
(3) 150g of yellow-white solid powder is heated to 120 ℃, and 50g of recrystallization solvent is dropwise added while stirring, wherein the recrystallization solvent is formed by mixing 20g of tetraethylene glycol dimethyl ether and 30g of 2-methyl-2,4-pentanediol. Continuously stirring for 2h, and cooling to obtain white viscous paste, i.e. high-viscosity paste.
(4) 100g of the high-viscosity paste prepared in the step (3) is heated to 80 ℃, 17g of organic acid active agent, 8g of surfactant and 6g of corrosion inhibitor are added while stirring, wherein the organic acid active agent consists of 6g of succinic acid, 5g of dimethylolpropionic acid and 6g of ricinoleic acid, the surfactant consists of 4g of polyethylene glycol octyl phenyl ether and 4g of dibromobutylene glycol, and the corrosion inhibitor consists of 3g of 1,2,3 benzotriazole and 3g of benzimidazole.
(5) And continuously heating and stirring for 2h, cooling, and placing in a low-temperature drying environment at the temperature of 2-5 ℃ for 24h for aging to obtain a light yellow paste, namely the prepared paste-shaped soldering flux.
Example 2
The embodiment provides a preparation method of a high-viscosity low-residue soldering flux, which comprises the following steps:
(1) Heating 60gKR rosin and 100g dodecanedioic acid to 100 ℃, keeping the temperature, fully stirring for 0.5h to obtain light yellow liquid, and cooling; adding 150g of dioxane into the light yellow liquid, heating to 100 ℃, uniformly stirring, and cooling to obtain a recrystallized crystal which is a composite paste.
(2) The prepared composite paste was taken out and heated to 120 ℃ and stirred using a stirrer with dispersion, while 15g of 1,4 butanediol and 25g of 1,5-pentanediol were slowly added dropwise. The stirring speed is adjusted to 1000r/min, after stirring and dispersing for 0.5h, 0.3g of concentrated sulfuric acid is dripped into a test tube and stirring is continued. And stopping stirring after 3h, cooling to obtain a light yellow reaction solution, distilling under reduced pressure, and cooling to obtain a light yellow solid. The yellowish powder was treated and washed with deionized water, and then dried under reduced pressure at a drying temperature of 50 ℃ to obtain a yellowish white solid powder.
(3) 150g of yellow-white solid powder is heated to 70 ℃, and 30g of recrystallization solvent is added dropwise while stirring, wherein the recrystallization solvent is formed by mixing 20g of 2-ethyl-1,3-hexanediol and 10g of triethylene glycol dimethyl ether. Continuously stirring for 1h, and cooling to obtain white viscous paste, i.e. high-viscosity paste.
(4) 100g of the high-viscosity paste prepared in the step (3) is taken and heated to 70 ℃, 20g of organic acid active agent, 5g of surfactant and 15g of corrosion inhibitor are added while stirring, wherein the organic acid active agent consists of 4g of 2,2-dimethylolpropionic acid, 10g of succinic acid and 6g of 2-picolinic acid, the surfactant consists of 5g of ST-400, and the corrosion inhibitor consists of 8g of 1,2,3 benzotriazole and 7g of 2-methyl benzimidazole.
(5) And continuously heating and stirring for 2h, cooling, placing in a low-temperature drying environment at the temperature of 2-5 ℃ for 24h, and aging to obtain a light yellow paste, namely the prepared paste-shaped soldering flux.
Example 3
The embodiment provides a preparation method of a high-viscosity low-residue soldering flux, which comprises the following steps:
(1) Heating 70g of dimerized rosin 95 and 50g of dodecanedioic acid to 180 ℃, keeping the temperature, fully stirring for 1h to obtain light yellow liquid, cooling, adding 130g of dioxane into the light yellow liquid, heating to 80 ℃, uniformly stirring, and cooling to obtain recrystallized crystals, wherein the crystals are composite paste.
(2) The prepared composite paste was taken out and heated to 150 ℃, stirred using a stirrer with dispersion, and 40g of propylene glycol and 40g of 1,5-pentanediol were slowly added dropwise. The stirring speed is adjusted to 1500r/min, after stirring and dispersing for 0.5h, 0.1g of concentrated sulfuric acid is dripped into a test tube and stirring is continued. And stopping stirring after 6 hours, cooling to obtain a light yellow reaction liquid, and distilling under reduced pressure and cooling to obtain a light yellow solid. The pale yellow powder was treated and washed with deionized water, then dried under reduced pressure at 65 ℃ to give a pale yellow solid powder.
(3) 150g of yellow-white solid powder is heated to 160 ℃, and 60g of recrystallization solvent is dropwise added while stirring, wherein the recrystallization solvent is formed by mixing 30g of tetraethylene glycol dimethyl ether and 30g of 2-methyl-2,4-pentanediol. Continuously stirring for 3h, and cooling to obtain white viscous paste, i.e. high-viscosity paste.
(4) Heating 100g of the high-viscosity paste prepared in the step (3) to 70 ℃, adding 10g of organic acid active agent, 10g of surfactant and 2g of corrosion inhibitor while stirring, wherein the organic acid active agent comprises 6g of succinic acid, 10g of succinic acid and 4g of dimethylolpropionic acid, the surfactant comprises 5g of polyethylene glycol octyl phenyl ether and 5g of phosphoric acid-2-ethylhexyl ester, and the corrosion inhibitor is 2g of benzimidazole.
(5) And continuously heating and stirring for 2h, cooling, and placing in a low-temperature drying environment at the temperature of 2-5 ℃ for 24h for aging to obtain a light yellow paste, namely the prepared paste-shaped soldering flux.
Example 4
The embodiment provides a preparation method of a high-viscosity low-residue soldering flux, which comprises the following steps:
(1) Heating 90g of dimerized rosin 95 and 70g of sebacic acid to 130 ℃, keeping the temperature, fully stirring for 1h to obtain a light yellow liquid, cooling, adding 80g of carbon tetrachloride into the light yellow liquid, heating to 120 ℃, uniformly stirring, and cooling to obtain recrystallized crystals, wherein the crystals are a composite paste.
(2) The prepared composite paste was taken out and heated to 135 ℃, stirred using a stirrer with dispersion, and 60g of 1,3-butanediol was slowly added dropwise. Adjusting the stirring speed to 1300r/min, stirring and dispersing for 0.5h, then dropwise adding 0.2g of concentrated sulfuric acid into a test tube, and continuing stirring. And stopping stirring after 4h, cooling to obtain a light yellow reaction solution, distilling under reduced pressure, and cooling to obtain a light yellow solid. The pale yellow powder was treated and washed with deionized water, and then dried under reduced pressure at 55 ℃ to give a pale yellow solid powder.
(3) 150g of yellow-white solid powder is heated to 95 ℃, and 50g of recrystallization solvent is dropwise added while stirring, wherein the recrystallization solvent is formed by mixing 20g of 2-ethyl-1,3-hexanediol, 20g of tetraethylene glycol dimethyl ether and 10g of triethylene glycol dimethyl ether. Continuously stirring for 2h, and cooling to obtain white viscous paste, i.e. high-viscosity paste.
(4) 100g of the high-viscosity paste prepared in the step (3) is taken and heated to 85 ℃, 15g of organic acid active agent, 7g of surfactant and 10g of corrosion inhibitor are added while stirring, wherein the organic acid active agent comprises 6g of 2,2-dimethylolpropionic acid, 4g of succinic acid and 5g of ricinoleic acid, the surfactant comprises 7g of dibromobutenediol, and the corrosion inhibitor comprises 5g of 1,2,3-benzotriazole and 5g of benzimidazole.
(5) And continuously heating and stirring for 2h, cooling, and placing in a low-temperature drying environment at the temperature of 2-5 ℃ for 24h for aging to obtain a light yellow paste, namely the prepared paste-shaped soldering flux.
Example 5
The embodiment provides a preparation method of a high-viscosity low-residue soldering flux, which comprises the following steps:
(1) Heating 40g of dimerized rosin 95, 30g of sebacic acid and 60g of tridecanedioic acid to 120 ℃, keeping the temperature and fully stirring for 0.8h to obtain light yellow liquid, cooling, adding 70g of petroleum ether into the light yellow liquid, heating to 50 ℃, uniformly stirring, and cooling to obtain recrystallized crystals, wherein the crystals are composite paste.
(2) The prepared composite paste was taken out and heated to 125 ℃, stirred by a stirrer with dispersion, and 50g of a crosslinking agent composed of 30g of 1,4-butanediol and 20g of 1,5-pentanediol was slowly dropped. Adjusting the stirring speed to 1100r/min, stirring and dispersing for 0.5h, dropwise adding 0.3g of concentrated sulfuric acid into a test tube, and continuously stirring. And stopping stirring after 5h, cooling to obtain a light yellow reaction solution, distilling under reduced pressure, and cooling to obtain a light yellow solid. The yellowish powder was treated and washed with deionized water, and then dried under reduced pressure at a drying temperature of 50 ℃ to obtain a yellowish white solid powder.
(3) 150g of yellow-white solid powder is heated to 140 ℃, and 45g of recrystallization solvent is added dropwise while stirring, wherein the recrystallization solvent is formed by mixing 15g of 2-methyl-2,4-pentanediol and 30g of triethylene glycol dimethyl ether. Continuously stirring for 3h, and cooling to obtain white viscous paste, i.e. high viscosity paste.
(4) 100g of the high-viscosity paste prepared in the step (3) is heated to 95 ℃, 18g of organic acid active agent, 8g of surfactant and 13g of corrosion inhibitor are added while stirring, wherein the organic acid active agent comprises 8g of dimethylolpropionic acid and 10g of ricinoleic acid, the surfactant comprises 5g of ST-400 and 8g of dibromobutenediol, and the corrosion inhibitor is 13g of 1,2,3-benzotriazole.
(5) And continuously heating and stirring for 2h, cooling, and placing in a low-temperature drying environment at the temperature of 2-5 ℃ for 24h for aging to obtain a light yellow paste, namely the prepared paste-shaped soldering flux.
Example 6
The embodiment provides a preparation method of a high-viscosity low-residue soldering flux, which comprises the following steps:
(1) Heating 65g of KR610 rosin, 40g of dodecanedioic acid and 40g of tridecanedioic acid to 165 ℃, keeping the temperature, fully stirring for 1h to obtain a light yellow liquid, cooling, adding 80g of petroleum ether into the light yellow liquid, heating to 110 ℃, uniformly stirring, and cooling to obtain a recrystallized crystal which is a composite paste.
(2) The prepared composite paste was taken out and heated to 140 ℃, stirred using a stirrer with dispersion, and 65g of a crosslinking agent consisting of 40g of propylene glycol and 25g of 1,3-butanediol was slowly added dropwise. The stirring speed is adjusted to 1400r/min, after stirring dispersion for 0.5h, 0.1g of concentrated sulfuric acid is added dropwise by a test tube and stirring is continued. And stopping stirring after 3h, cooling to obtain a light yellow reaction solution, distilling under reduced pressure, and cooling to obtain a light yellow solid. The yellowish powder is treated and washed with deionized water, and then dried under reduced pressure at 60 ℃ to obtain yellowish white solid powder.
(3) 150g of yellow-white solid powder is heated to 95 ℃, and 55g of recrystallization solvent is dropwise added while stirring, wherein the recrystallization solvent is formed by mixing 30g of 2-ethyl-1,3-hexanediol, 15g of diethylene glycol and 10g of triethylene glycol dimethyl ether. Continuously stirring for 2h, and cooling to obtain white viscous paste, i.e. high-viscosity paste.
(4) 100g of the high-viscosity paste prepared in the step (3) is heated to 80 ℃, 15g of organic acid active agent, 6g of surfactant and 7g of corrosion inhibitor are added while stirring, wherein the organic acid active agent comprises 5g of 2,2-dimethylolpropionic acid and 7g of succinic acid, the surfactant comprises 2g of polyethylene glycol octyl phenyl ether and 4g of phosphoric acid-2-ethylhexyl ester, and the corrosion inhibitor is 7g of 2-methyl styrene imidazole.
(5) And continuously heating and stirring for 2h, cooling, placing in a low-temperature drying environment at the temperature of 2-5 ℃ for 24h, and aging to obtain a light yellow paste, namely the prepared paste-shaped soldering flux.
Example 7
This example is substantially the same as example 1, except that: the resin acid monomer is directly reacted with the cross-linking agent without being recrystallized.
Comparative example 1
The paste flux of the comparative example is a commercial paste flux B on the market.
Experimental example 1
A commercially available paste flux B on the market, referred to in examples 1-7 and comparative example 1, was applied using SAC305 metal powder No. 3 as a paste: metal powder =86 mass ratio of 14, and the viscosity, collapse resistance, and spreading rate of the solder paste were tested. Wherein, the viscosity test method of the solder paste refers to JIS-Z-3284, the collapse resistance test method refers to JIS-Z-3284, and the spreading ratio test method refers to JIS-Z-3197. The performance indices are recorded in the table below.
TABLE 1 Properties of the experimental groups
As can be seen from the table above, compared with the comparative example, the soldering flux prepared by the embodiment of the application has higher viscosity, better collapse resistance and better spreading rate, which all provide more powerful guarantee for the welding strength.
Experimental example 2
The flux obtained in example 1 was subjected to a soldering test in accordance with JIS-Z-3197. And shooting a micro-topography image of the welding point after welding. As shown in fig. 1 and 2. From the gold phase diagram of the solder paste welding spot in the figures 1 and 2, the gold phase structure of the solder paste prepared by the invention after welding is fine and smooth, and no obvious air holes are generated.
Experimental example 3
Spreading experiments were carried out with the solder pastes prepared by the paste flux in example 1 and comparative example 1, in accordance with the method of JIS-Z-3197, while observing post-weld residue and carbon deposition around the solder joints, as shown in fig. 3 and 4. As can be seen from the figure, the solder paste prepared by the invention has less residue around the solder joint after welding and no carbon deposition. The residual around the solder paste welding point (such as around A, B point) prepared by the paste flux of comparative example 1 is serious, and the carbon deposition is obvious, which is mainly caused by the carbonization of the thixotropic agent or the coupling agent used in the paste flux after high-temperature welding.
In conclusion, the preparation method of the high-viscosity paste for the soldering flux provided by the application has the following advantages:
(1) The carboxyl of the resin acid monomer and the hydroxyl of the cross-linking agent are subjected to cross-linking reaction, so that the acid value of the paste soldering flux is greatly reduced, the corrosivity and the moisture absorption of the paste are reduced, and the storage performance of the paste soldering flux or the tin paste prepared from the paste soldering flux is improved. At the welding temperature (above 300 ℃), the carboxyl of the paste is released again, so that the acid value of the paste soldering flux is improved, and the oxide film removing capability of the paste soldering flux is enhanced.
(2) The paste does not contain polymers such as coupling agents, thixotropic agents and the like which are difficult to volatilize and decompose at high temperature, and the residues after welding are greatly reduced. But because the molecules of paste-forming polymers in the paste are subjected to a cross-linking reaction, the paste soldering flux or the solder paste prepared from the paste soldering flux has high viscosity and good collapse resistance, and the prepared solder paste is particularly suitable for hot air spot coating automatic welding.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-viscosity paste for soldering flux is characterized by comprising the following steps:
mixing 120-160 parts by weight of resin acid monomer and 40-80 parts by weight of cross-linking agent to perform esterification cross-linking reaction to generate an esterification cross-linking product, wherein the resin acid monomer is selected from at least one of KR610 rosin, dimerized rosin 95, dodecanedioic acid, sebacic acid and tridecanedioic acid; the cross-linking agent comprises at least one of propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol;
and mixing the esterified crosslinking product with a paste forming solvent according to the mass ratio of 150.
2. The method of claim 1, wherein the esterified crosslinked product is mixed with the paste-forming solvent in such a manner that:
heating the esterified crosslinking product to 70-160 ℃, and then dropwise adding the paste-forming solvent into the esterified crosslinking product while stirring;
preferably, the paste forming solvent is selected from at least two of 2-ethyl-1,3-hexanediol, tetraethylene glycol dimethyl ether, diethylene glycol, 2-methyl-2,4-pentanediol, and triethylene glycol dimethyl ether.
3. The method of claim 1, further comprising, prior to the esterification crosslinking reaction: recrystallizing the resin acid monomer;
the recrystallization mode is as follows: the resin acid monomer and the recrystallization solvent are mixed and heated to 50-120 ℃ according to the mass ratio of 80-160, are uniformly stirred and mixed, and are subjected to a recrystallization step to obtain a composite paste containing the resin acid monomer;
mixing the resin acid monomer with the cross-linking agent is to mix the composite paste with the cross-linking agent;
preferably, the resin acid monomer is heated to 100-180 ℃ for melting before being mixed with the recrystallization solvent, and is cooled after being stirred for 0.5-1 h; the resin acid monomer mixed with the recrystallization solvent is a resin acid monomer after heating, melting and cooling;
preferably, the heating mode is heating by a silicone oil bath;
preferably, the recrystallization solvent is selected from at least one of dioxane, carbon tetrachloride and petroleum ether.
4. The method according to claim 1, wherein the mixing of the resin acid monomer and the crosslinking agent to perform the esterification crosslinking reaction is:
heating the resin monomer to 120-150 ℃, continuously dispersing, stirring and dripping the cross-linking agent at the temperature, and adding 0.01-0.03 part of catalyst after the dripping of the cross-linking agent is finished for 20-40 min and continuously stirring for 3-6 h;
preferably, the catalyst is concentrated sulfuric acid;
preferably, the stirring rate is 1000 to 1500r/min.
5. The preparation method according to claim 1, wherein a light yellow reaction solution is obtained after the esterification crosslinking reaction, the esterification crosslinking reaction further comprises an esterification crosslinking product extraction step from the light yellow reaction solution, and the esterification crosslinking product extraction step comprises:
distilling the light yellow reaction liquid under reduced pressure, and cooling to obtain a yellowish white solid primary esterification crosslinking product;
washing the primary esterification crosslinking product by using deionized water, and then drying under reduced pressure to obtain the esterification crosslinking product;
preferably, the drying temperature is 45 to 65 ℃.
6. A high-viscosity paste for a soldering flux, which is prepared by the preparation method according to any one of claims 1 to 5.
7. The high-viscosity low-residue soldering flux is characterized by comprising the following components in parts by weight: 100 parts of the high-viscosity paste body as claimed in claim 6, 10 to 20 parts of organic acid activator, 5 to 10 parts of surfactant and 2 to 15 parts of corrosion inhibitor; the organic acid active agent is selected from at least one of 2,2-dimethylolpropionic acid, succinic acid, dimethylolpropionic acid, ricinoleic acid and 2-picolinic acid, the surfactant is selected from at least one of ST-400, polyethylene glycol octyl phenyl ether, dibromobutylene glycol and 2-ethylhexyl phosphate, and the corrosion inhibitor is selected from at least one of 1,2,3-benzotriazole, 2-methyl benzimidazole and benzimidazole;
preferably, the organic acid active agent is selected from at least two of 2,2-dimethylolpropionic acid, succinic acid, dimethylolpropionic acid, ricinoleic acid and 2-picolinic acid.
8. The method of preparing a highly viscous, low residue flux of claim 7, comprising:
heating the high-viscosity paste to 70-100 ℃, and adding the organic acid active agent, the surfactant and the corrosion inhibitor while stirring; stirring and mixing for 1.5-2.5 h, cooling, and aging in a low-temperature drying environment at 2-5 ℃ for 20-30 h to obtain the high-viscosity low-residue soldering flux.
9. A solder paste comprising the high viscosity and low residue flux of claim 7 or the high viscosity and low residue flux prepared by the method of claim 8.
10. The high viscosity and low residue soldering flux as defined in claim 7, the high viscosity and low residue soldering flux prepared by the preparation method as defined in claim 8 or the solder paste as defined in claim 9.
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